- Radical-initiated polyolefinic cyclizations in linear triquinane synthesis. Model studies and total synthesis of (±)-hirsutene
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Details of a novel radical-initiated polyolefinic cyclization approach to linear condensed cyclopentanoids are reported. The strategy is executed in three stages: (1) S(n)2'-anti opening of a vinyl lactone to produce a trans-3,5-disubstituted cyclopentene, (2) rapid elaboration to a cyclization precursor, and (3) single step tandem radical cyclization to produce a cis-anti-cis tricyclo[3.3.0]undecane. Model substrates 16a and 16b give high yields of tricyclic products 17 and 18, respectively. An effort to rationalize the interesting endo selectivity via the Beckwith transition state model is proposed. Cyclizations of 28 and 29 to 30 and 31 demonstrate the viability of a tandem hexenyl-hexynyl cyclization. The work culminates with a total synthesis of (±)-hirsutene. A selective approach to methyl substituted vinyl lactones by Claisen rearrangement-phenylselenolactonization-elimination of acetoxy cyclopentenols is exemplified by the synthesis of 12. Tandem cyclization of 38 produces hirsutene (1) in a single step. Alternatively, cyclization of 37 yields trimethylsilyl hirsutene.
- Curran,Rakiewicz
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Read Online
- Diastereoselective synthesis of 2H,5H-dihydrofurans by cobalt-mediated cycloisomerization of allyl propargyl ethers. Application to poly-THF molecules
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(Matrix Presented) Allyl propargyl ethers undergo cobalt-mediated cycloisomerization reactions to form dihydrofurans in good yield and with excellent diastereoselectivity. The reaction works with a range of substrates, and its utility in synthesis is exem
- Ajamian, Alain,Gleason, James L.
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Read Online
- Formation of Alkynylgermyl-Substituted Germylenes via a Catenation of Ge Atoms
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Reactions of amidinate-stabilized germylene chlorides R1Ge(:)Cl (R1 = PhC(NtBu)2) and R2Ge(:)Cl (R2 = PhC(NCy)2, Cy = cyclohexanyl) with trimethylsilylethynyl lithium salt (LLi, L = a'C?f‰CTMS) afforded alkynylgermylsubstituted germylenes R1(:)Ge-GeL3 (1) and [R2GeL2]2Ge(:) (2), respectively. Both of them may undergo the formation of Gea'Ge single bonds with a concomitant 1,2-shift of ethynyl groups. DFT calculations determined the reaction pathways where two possible intermediates (:)GeL2 and RGe(:)L (R = R1, R2) are proposed, which were consistent with the trapping reactions of (:)GeL2 toward IAra(:)GeL2 (3, IAr = :C{N(Ar)CH}2, Ar = 2,6-iPr2C6H3). The reaction of 1 with N3TMS gave a new aminogermylene R1(:)Gea'N(TMS)-GeL3 (4), indicating a reactive Gea'Ge bond.
- Liu, Chenghuan,Zhu, Keke,Han, Weichun,Liu, Xue,Zhang, Zheng-Feng,Su, Ming-Der,Wu, Di,Li, Yan
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Read Online
- METHODS TO PRODUCE ORGANOTIN COMPOSITIONS WITH CONVENIENT LIGAND PROVIDING REACTANTS
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Synthesis reactions are described to efficiently and specifically form compounds of the structure RSnL3, where R is an organic ligand to the tin, and L is hydrolysable ligand or a hydrolysis product thereof. The synthesis is effective for a broad range of R ligands. The synthesis is based on the use of alkali metal ions and optionally alkaline earth (pseudo-alkaline earth) metal ions. Compounds are formed of the structures represented by the formulas RSn(C≡CSiR'3)3, R'R"ACSnL3, where A is a halogen atom (F, Cl, Br or I) or an aromatic ring with at least one halogen substituent, R'R"(R'"O)CSnL3 or R'R"(N≡C)CSnZ3.
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Page/Page column 32-33
(2022/03/09)
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- Pd-catalyzed sp-sp3cross-coupling of benzyl bromides using lithium acetylides
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Organolithium-based cross-coupling reactions have emerged as an indispensable method to construct C-C bonds. These transformations have proven particularly useful for the direct and fast coupling of various organolithium reagents (sp, sp2, and sp3) with aromatic (pseudo) halides (sp2). Here we present an efficient method for the cross-coupling of benzyl bromides (sp3) with lithium acetylides (sp). The reaction proceeds within 10 min at room temperature and can be performed in the presence of organolithium-sensitive functional groups such as esters, nitriles, amides and boronic esters. The potential application of the methodology is demonstrated in the preparation of key intermediates used in pharmaceuticals, chemical biology and natural products.
- Buter, Jeffrey,Doze, Anna M.,Feringa, Ben L.,Mondal, Anirban,Visser, Paco
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supporting information
p. 7529 - 7532
(2021/08/05)
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- LIPID PRODRUGS OF GLUCOCORTICOIDS AND USES THEREOF
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The present invention provides lymphatic system-directing lipid prodrugs, pharmaceutical compositions thereof, methods of producing such prodrugs and compositions, and methods of improving the bioavailability or other properties of a therapeutic agent that comprises part of the lipid prodrug. The present invention also provides methods of treating a disease, disorder, or condition such as those disclosed herein, comprising administering to a patient in need thereof a disclosed lipid prodrug or a pharmaceutical composition thereof.
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Paragraph 00413; 00416
(2020/09/12)
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- Intramolecular Pd-Catalyzed Formal anti-Carboalkoxylation of Alkynes: Access to Tetrasubstituted Enol Ethers
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An intramolecular Pd-catalyzed formal anti-carboalkoxylation reaction is presented that provides access to tetrasubstituted enol ethers. The key to success is a cascade consisting of a formal anti-carbopalladation of a carbon–carbon triple bond followed by a nucleophilic attack of a hydroxy group at the emerging vinyl organopalladium species. The desired transformation proceeded smoothly with primary, secondary, and tertiary alcohols, and even with phenols. Depending on the substitution pattern of the enol ethers, a further Tsuji–Trost-type step may occur resulting in oligocyclic ketals.
- Schitter, Theresa,Jones, Peter G.,Werz, Daniel B.
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supporting information
p. 13446 - 13449
(2018/09/21)
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- Redox-Disproportionation of a Decamethyltitanocene(III) Isonitrile Alkynyl Complex
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A mixed decamethyltitanocene(III) isonitrile alkynyl complex (7) was synthesized by the sequential introduction of the isonitrile and alkynyl ligands. Direct synthesis results in the formation of the diamagnetic decamethyltitanocene bis(isonitrile) (2) an
- Rei?, Fabian,Altenburger, Kai,Hollmann, Dirk,Spannenberg, Anke,Jiao, Haijun,Arndt, Perdita,Rosenthal, Uwe,Beweries, Torsten
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supporting information
p. 7891 - 7895
(2017/06/19)
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- MACROPHAGE IDENTIFICATION AGENT, AND IDENTIFICATION METHOD, SORTING METHOD, EVALUATION METHOD, SCREENING METHOD AND KIT USING THE MACROPHAGE IDENTIFIER AGENT
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An object of the present invention is to provide an identification method for a macrophage subtype using an organic compound. Another object of the present invention is to provide a macrophage identification agent containing an organic compound in which a spectral characteristic obtained when the organic compound is added is different depending on a macrophage subtype. Still another object of the present invention is to provide an evaluation method for a macrophage subtype using a macrophage identification agent, an analysis method for correlation between a macrophage subtype and a test substance, a screening method for correlation between a macrophage subtype and a test substance, and a kit. An identification method for a macrophage subtype utilizing that a spectral characteristic obtained with an organic compound added is different depending on a macrophage subtype is provided.
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Paragraph 0434-0436
(2016/02/28)
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- Carbon monoxide-isocyanide coupling promoted by acetylide addition to a diiron complex
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C-N bond formation involving carbon monoxide and isocyanide ligands is promoted by addition of a series of lithium acetylides to a diiron μ-aminocarbyne complex, i.e. [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO)(CNXyl)(Cp)2][SO3CF3
- Marchetti, Fabio,Zacchini, Stefano,Zanotti, Valerio
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supporting information
p. 8101 - 8104
(2015/05/20)
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- Fluorovinyl Thioethers as Putative Steric and Electronic Thioester Enolate Mimetics: Chemoselective HF Addition to Acetylene Thioethers
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Fluorovinyl thioethers are presented as a putative biomimetic surrogate for the enol/ate of a thioester. A method is explored for the preparation of fluorovinyl thioethers by treatment of acetylene thioethers with pyridinium (poly)-hydrogen fluoride. Titr
- Bello, Davide,Cormanich, Rodrigo A.,O'Hagan, David
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- Selective Oligomerization and [2 + 2 + 2] Cycloaddition of Terminal Alkynes from Simple Actinide Precatalysts
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A catalyzed conversion of terminal alkynes into dimers, trimers, and trisubstituted benzenes has been developed using the actinide amides U[N(SiMe3)2]3 (1) and [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)N(SiMe3)] (An = U (2), Th (3)) as precatalysts. These complexes allow for preferential product formation according to the identity of the metal and the catalyst loading. While these complexes are known as valuable precursors for the preparation of various actinide complexes, this is the first demonstration of their use as catalysts for C-C bond forming reactions. At high uranium catalyst loading, the cycloaddition of the terminal alkyne is generally preferred, whereas at low loadings, linear oligomerization to form enynes is favored. The thorium metallacycle produces only organic enynes, suggesting the importance of the ability of uranium to form stabilizing interactions with arenes and related π-electron-containing intermediates. Kinetic, spectroscopic, and mechanistic data that inform the nature of the activation and catalytic cycle of these reactions are presented. (Chemical Equation Presented).
- Batrice, Rami J.,McKinven, Jamie,Arnold, Polly L.,Eisen, Moris S.
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p. 4039 - 4050
(2015/09/01)
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- PHOSPHOHISTIDINE ANALOGS
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The present invention relates to the phosphohistidine analogs of the present invention which of the formula (I) and the hapten containing the residue of same. It also relates to the hapten conjugated to a carrier molecule and the isolated antibodies raise
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Page/Page column 59-60
(2012/04/10)
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- Total synthesis of (-)-isatisine A
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A modular total synthesis of (-)-isatisine A is described in which four consecutive metal-mediated transformations have been employed at the final stage. These include [Pd]-catalyzed Sonogashira coupling, [Pd]-catalyzed nitroalkyne cycloisomerization leading to isatogens, and addition of indoles to isatogens using InCl3-and [Rh]-catalyzed oxidative N-heterocyclization of amino alcohol to form the key amide bond. In addition to these, the removal of the protecting groups has also been carried out in a selective fashion employing either catalytic or stoichiometric metal/metal-based reagents.
- Patel, Pitambar,Ramana
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p. 10509 - 10515
(2013/02/23)
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- Diastereoselective synthesis of 3,3-disubstituted oxindoles from atropisomeric N-aryl oxindole derivatives
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Diastereoselective synthesis of 3,3-disubstituted oxindoles has been examined by transformations involving nucleophilic addition, alkylation, and cycloaddition using chiral racemic N-aryl oxindoles bearing C-N axial chirality. The most striking features of this approach are high diastereoselectivities (up to >95:5) when using ortho-monosubstituted N-aryl oxindoles and easy removal of the p-(benzyloxy)aryl moiety in the axially twisted amides by a mild two-step sequence.
- Nakazaki, Atsuo,Mori, Ayako,Kobayashi, Susumu,Nishikawa, Toshio
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supporting information
p. 7131 - 7134
(2013/01/15)
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- COORDINATION COMPOUNDS OF THE BORON GROUP
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A coordination compound of an element of the boron group, the production of the compound and methods of using the compound as an additive, stabilizer, catalyst, co-catalyst, activator for catalyst systems, conductivity improver, and electrolyte.
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Page/Page column 5
(2010/03/02)
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- Application of an enyne metathesis/diels-alder cycloaddition sequence: A new versatile approach to the syntheses of C-Aryl glycosides and spiro- C-Aryl glycosides
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An efficient approach for the synthesis of a variety of C-aryl and spiro- C-aryl glycosides is described. This diversity-oriented strategy employed here relies on a sequential enyne metathesis to generate the 1,3-diene moiety and Diels-Alder reaction with
- Subrahmanyam, Ayyagari V.,Palanichamy, Kalanidhi,Kaliappan, Krishna P.
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supporting information; experimental part
p. 8545 - 8556
(2010/09/08)
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- Alkylative carbocyclization of ω-iodoalkynyl tosylates with alkynyllithium compounds through a carbenoid-chain process leading to (1-iodoprop-2-ynylidene)tetrahydrofurans and-cyclopropanes
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Alkylative carbocyclization reactions of ω-iodoalkynyl tosylates with alkynyllithium compounds to give products with incorporated iodine atoms are described. Slow addition of 2-(3-iodoprop-2-ynyloxy)ethyl tosylates to 1-alkynyllithium compounds in tetrahy
- Harada, Toshiro,Imaoka, Daisuke,Kitano, Chie,Kusukawa, Takahiro
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experimental part
p. 9164 - 9174
(2010/09/15)
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- METHOD FOR PRODUCING 4'-ETHYNYL d4T
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Disclosed is a method for mass-producing 4'-ethynyl d4T (4'-ethynyl-2',3'-didehydro-3'-deoxythymidine) by a simpler process at low cost. Specifically disclosed is a method for producing 4'-ethynyl d4T, which is characterized by comprising a step for introducing a triple bond-containing group into a furfuryl alcohol derivative or a levoglucosenone, by reacting the furfuryl alcohol derivative or levoglucosenone with a certain compound, and a step for reacting a compound represented by the formula (III), which is obtained by the aforementioned step, with thymine.
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Page/Page column 14
(2010/10/01)
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- GLUCOCORTICOID MIMETICS, METHODS OF MAKING THEM, PHARMACEUTICAL COMPOSITIONS, AND USES THEREOF
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Compounds of Formula I wherein R1, R2, X, and Y are as defined herein, or a tautomer, optical isomer, prodrug, co-crystal, or salt thereof; pharmaceutical compositions containing such compounds, and methods of modulating the glucocorticoid receptor function and methods of treating disease-states or conditions mediated by the glucocorticoid receptor function or characterized by inflammatory, allergic, or proliferative processes in a patient using these compounds.
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Page/Page column 81
(2009/12/28)
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- CATHEPSIN CYSTEINE PROTEASE INHIBITORS
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The present invention relates to novel compounds of the formula (I), wherein R'-R7, X, Y, D and n are as defined in the specification. These compounds are cysteine protease inhibitors which include but are not limited to inhibitors of cathepsms K, L, S an
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Page/Page column 72-73
(2008/12/04)
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- Reactivity of individual organolithium aggregates: A RINMR study of n-butyllithium and 2-methoxy-6-(methoxymethyl)phenyllithium
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Low-temperature rapid injection NMR (RINMR) experiments were performed on two lithium reagents, n-butyllithium and 2-methoxy-6-(methoxymethyl)phenyllithium (5), with the goal of measuring the relative reactivity of the different aggregates (dimer, mixed dimer, and tetramer for n-BuLi, monomer and tetramer for 5) toward typical electrophiles. The reaction of the n-BuLi dimer with (trimethylsilyl)acetylene first forms the mixed dimer n-BuLi·Me3SiC≡CLi, which is about 1/60 as reactive as the n-BuLi homodimer. The tetramer does not react. In the deprotonation of (phenylthio)acetylene, the n-BuLi dimer was found to be 3.5 × 108 as reactive as the tetramer, and in the addition to p-diethylaminobenzaldehyde, the relative reactivity was at least 2 × 104. In the deprotonation of (p-tolylsulfonyl)acetylene, the monomer of 5 was at least 1014 times as reactive as the tetramer. These measurements show that the difference in reactivity between the lower and higher aggregates of organolithium reagents can be many orders of magnitude higher than all previous estimates. Copyright
- Jones, Amanda C.,Sanders, Aaron W.,Bevan, Martin J.,Reich, Hans J.
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p. 3492 - 3493
(2008/01/01)
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- NOVEL B1 BRADYKININ RECEPTOR ANTAGONISTS
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The invention encompasses novel compounds of a formula I and pharmaceutically acceptable derivatives thereof, pharmaceutical compositions and methods for treatment of diseases mediated by B1 bradykinin receptor.
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Page/Page column 53
(2010/11/08)
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- Heterocyclic mchr1 antagoists
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This invention relates to novel heterocycles which are antagonists at the melanin-concentrating hormone receptor 1 (MCHR1), also referred to as 11 CBy, to pharmaceutical compositions containing them, to processes for their preparation, and to their use in
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Page/Page column 51
(2010/11/24)
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- AVERMECTIN AND AVERMECTIN MONOSACCHARIDE SUBSTITUTED IN THE 4”- AND 4’- POSITION RESPECTIVELY
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A compound of the formula (I) wherein the bond between carbon atoms 22 and 23 indicated with a broken line is a single or double bond, m is 0 or 1, R1 represents a C1-C12alkyl, C3-C8cycloalkyl or Csu
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Page/Page column 96
(2008/06/13)
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- TERTIARY AMINE AND METHOD FOR PRODUCING THE SAME
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PROBLEM TO BE SOLVED: To provide a new tertiary amine and a method for easily producing the tertiary amine in improved yield. SOLUTION: The tertiary amine is expressed by general formula (1) and produced by adding a thioamide expressed by general formula
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Page/Page column 16
(2010/02/10)
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- An unusual domino retro-ene-Conia reaction: Regio- and stereoselective one-carbon ring expansion of fenchol derivatives
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The 2-exo-substituted fenchol derivatives 1-7, easily prepared from (-)-fenchone in good-to-excellent yields, were pyrolyzed by dynamic gas-phase thermo-isomerization (DGPTI). At temperatures of ca. 620°, the substrates with a hydroxyallyl (1-4) or a hydr
- Rueedi, Georg,Laikov, Dimitri N.,Hansen, Hans-Juergen
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p. 1990 - 2021
(2007/10/03)
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- ACETYLENE COMPOUNDS
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The present invention is concerned with certain adenosine derivatives having an acetylene group attached in the 5' position by a linker, which are adenosine A1 agonists, and to their use in therapy.
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- Alkynyl S, N-acetal derivative and method of producing the same
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An alkynyl S,N-acetal derivative of the present invention is represented by the following structural formula: In the structural formula, R1 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a silyl group, or an alkyny
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- Tertiary amine and method for producing the same
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The present invention relates to a method for easily producing a tertiary amine with high yield. A tertiary amine represented by general formula (1) is produced by adding a metal-containing reagent represented by general formula (6) into a reaction system
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- MACROCYCLIC COMPOUNDS USEFUL AS PHARMACEUTICALS
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The present invention provides compounds having formula (I), and additionally provides methods for the synthesis thereof and methods for the use thereof in the treatment of various disorders including inflammatory or autoimmune disorders, and disorders involving malignancy or increased angiogenesis, wherein R1 -R11, t, X, Y, Z, and n are as defined herein.
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Page/Page column 110
(2010/02/07)
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- Synthesis of unsymmetrically substituted 1,3-butadiynes and 1,3,5-hexatriynes via alkylidene carbenoid rearrangements
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Unsymmetrically substituted 1,3-butadiynes and 1,3,5-hexatriynes are synthesized in four steps from commercially available aldehydes or carboxylic acids. The key step in this process involves a Fritsch-Buttenberg-Wiechell rearrangement, in which an alkylidene carbenoid intermediate subsequently rearranges to the desired polyyne. This rearrangement proceeds under mild conditions, and it is tolerant of a range of functionalities. In general, the procedurally facile formation of the dibromoolefinic precursors, in combination with the effectiveness of the rearrangement step, makes this procedure an attractive alternative to traditional methods for di- and triyne synthesis that utilize palladium or copper catalysis.
- Shi Shun, Annabelle L. K.,Chernick, Erin T.,Eisler, Sara,Tykwinski, Rik R.
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p. 1339 - 1347
(2007/10/03)
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- Diastereoselective synthesis of heterosubstituted organogembismetallic reagents. Application to a new propargylmetalation reaction of vinyl metals
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The allylzincation and propargylzincation of various γ-heterosubstituted vinyl metals proceed diastereoselectively. This represents a new synthetic approach to construct two or three adjacent stereogenic centers in acyclic systems.
- Brasseur, Denis,Marek, Ilane,Normant, Jean-F.
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p. 7235 - 7250
(2007/10/03)
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- Asymmetric Synthesis Using Chiral Acetals: Studies on the Nucleophilic Addition of Organometallics to Chiral α-Keto Acetals in Open-Chain Systems
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Nucleophilic addition of organometallic reagents (Grignard reagents and organolithium reagents) to three chiral α-keto acetals (1a-c) in open-chain systems was studied.The reactions of the chiral α-keto acetals (1a,1b) having a chiral auxiliary as a keton
- Tamura, Yasumitsu,Annoura, Hirokazu,Fuji, Masahiro,Yoshida, Takayuki,Takeuchi, Ritsuko,Fujioka, Hiromichi
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p. 4736 - 4746
(2007/10/02)
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- A NOVEL SYNTHESIS OF THE α-HYDROXYKETONE MOIETY OF ANTHRACYCLINONES BY THE USE OF 2-TRIMETHYLSILYLETHYNYLCERIUM(III) REAGENTS
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2-trimethylsilylethynylcerium(III) reagents were found to efficiently react with 1,2,3,4-tetrahydronaphthalene-2-one derivatives, giving the corresponding adducts in high yields.Hydration of the adducts readily afforded the α-hydroxy methyl ketones which are versatile synthetic intermediates of natural and unnatural anthracyclinones.
- Suzuki, Michiyo,Kimura, Yoshikazu,Terashima, Shiro
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p. 1543 - 1546
(2007/10/02)
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- Neue Anwendungsmoeglichkeiten fuer schwere Hauptgruppenelemente in der organischen Synthese
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Ausser Elementen der 2.Reihe und einem Element der 3.Reihe des Periodensystem - Si,P,S bzw.Se -, deren Organoelementgruppen wie Me3Si und Ph3P+ sich vielfach bewaehrten, koennen in der organischen Synthese auch andere Elemente der 3. sowie der
- Kauffmann, Thomas
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p. 401 - 420
(2007/10/02)
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